MXPA00009601A - Detergent compositions. - Google Patents

Detergent compositions.

Info

Publication number
MXPA00009601A
MXPA00009601A MXPA00009601A MXPA00009601A MXPA00009601A MX PA00009601 A MXPA00009601 A MX PA00009601A MX PA00009601 A MXPA00009601 A MX PA00009601A MX PA00009601 A MXPA00009601 A MX PA00009601A MX PA00009601 A MXPA00009601 A MX PA00009601A
Authority
MX
Mexico
Prior art keywords
polymer
surfactant
composition
gel
composition according
Prior art date
Application number
MXPA00009601A
Other languages
Spanish (es)
Inventor
Michael Paul Aronson
Original Assignee
Unilever Nv
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10829868&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=MXPA00009601(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever Nv filed Critical Unilever Nv
Publication of MXPA00009601A publication Critical patent/MXPA00009601A/en

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/042Gels
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0094High foaming compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2041Dihydric alcohols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2065Polyhydric alcohols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/228Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing groups
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Emergency Medicine (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Molecular Biology (AREA)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

An aqueous detergent composition, which is in the form of a thickened, mobile fluid, comprising foaming detergent and a polymer or polymer mixture which is capable of forming a reversible gel, which polymer or mixture is present in the composition as a multiplicity of individual gel particles.

Description

DETERGENT COMPOSITIONS This invention relates to foaming detergent compositions that can be used for personal washing or other applications. A variety of detergent products for personal washing have a formula of viscous liquids, creams or gel. Examples of these products are shampoo for hair, bath gel and facial washes. Generally, these products contain foaming surfactants which usually comprise at least 3% by weight of the anionic surfactant, possibly accompanied by some amphoteric, two-ionic or non-ionic surfactant. It is very usual that these products contain one or more ingredients whose function is to increase the viscosity of the composition. Some other liquid detergent compositions also need to contain a foaming surfactant and have a viscosity greater than that of water. One possibility to improve the viscosity of the fluid composition is to incorporate a sufficient amount of electrolyte together with a sufficient amount of a selected surfactant, so that the surfactant is present in a viscous phase and thereby increase the viscosity of the resulting composition. It is also known to incorporate polymeric materials to improve the viscosity. One category of the synthetic polymers used for this purpose are crosslinked polyacrylates, for example, those marketed under the brand name Carbopol. Natural polymers have also been used for this purpose and in particular xanthan gum and its derivatives have been used. Personal wash products, especially shampoos, which contain xanthan gum are described, for example, in US-A-5151210 and EP-A-500423. Detergent products containing other polymers are described, for example, in US-A-5286405 and GB-A-2188060. EP-A-271131 discloses a variety of products that are intended to be applied to the skin, which are thickened with carrageenan to form gels. Many of these do not include surfactants. A product discovered in this document is a cleaning composition, which contains a low foaming nonionic surfactant. WO 98/08601 discloses hydrogel particles / dispersions which are capable of trapping water insoluble beneficial agents and gently disintegrating them to impart desirable characteristics of use. GB-1, 461,775 discloses aqueous detergent compositions, in the liquid state containing stable suspended particles that disintegrate when the composition is diluted in water. EP-A-0355908 discloses a liquid-based composition comprising at least one gellable polysaccharide which is capable of forming a reversible gel.
JP-A-9078083 discloses a detergent composition comprising one or more glycerin derivatives, such as carraginin and one or more anionic and non-anionic water soluble polymers. JP-A-8283123 discloses compositions comprising specific amounts of nonionic surfactants, polyhydric alcohol, an ether glycol and a water insoluble polymer. JP-A-8310942 discloses aqueous gel-like detergent compositions comprising a polyoxyethylene alkyl ester, carrageenan, water and a polyol. JP-A-6264090 discloses liquid detergent compositions comprising an N-acyl glutamate and at least one natural polysaccharide such as carrageenan. JP-A-2123193 discloses compositions comprising specific amounts of alkyl glucoside and one or more high molecular compounds soluble in water such as kappa carrageenan. EP-A-0445659 discloses a hair setting composition comprising specific amounts of carrageenan and an addition of non-ionic surface active agent-type oxide ethylene. WO 84/04039 discloses sanitary formulas that include low molecular extracts of carrageenin in amounts that provide abundance to the hair and keratin for the skin and conditioning of hair and skin as a result of its ability to bind to water.
WO 80/01142 discloses an adjuvant containing iota-carragginine, a gel-inducing cation and a selected anionic, non-ionic or amphoteric surfactant, which forms a concentrated emulsion when mixed with water and water-insoluble liquids or solids of low fusion. A variety of polymers of biological origin, when found in an aqueous solution, have the ability to form so-called reversible gels, which fuse when heated but are again converted to gel subsequently when cooled. A well-known example of a polysaccharide that forms reversible gels is agar. An aqueous solution containing a small percentage of agar is a liquid that when mobile is hot, but when allowed to cool forms a gel with sufficient rigidity to maintain its own shape. Other polymers that are found in natural form that can form reversible gels are carrageenan, furceleran, gelan and pectin. The formulation of gels by natural polysaccharides arises from the interaction between the molecules of the polymers. Reversible gels generally have a melting temperature or temperature range, referred to as the gelation temperature. This is the temperature at which, with a low heating, it is observed that the gel fuses while this interaction disappears quickly. In this way, on the gelation temperature, the hot solution of the polymer is mobile. When cooled below its gelation temperature, the interaction of the polymer molecules allows them to form in a continuous and branched crosslinking that extends through the sample. Contrary to the formation of a continuous, branched crosslinking, certain materials that thicken water, do so only through a transient entanglement of molecules. A discussion on polysaccharide gels, including their range of mechanical properties, is found in "Gels and Gelling," by Allan H. Clark, which makes up chapter 5 of Physical Chemistry of Food, Schwartzberg and Hartel, editors, published by Marcel Dekker, 1992. In some cases there is hysteresis and the setting and melting temperatures are not identical. The melting temperature of a gel can be adequately measured by placing a steel ball, with a diameter of about 1 mm, on the surface of a fully set sample, then raising the temperature slowly, for example, in a programmable water bath . The melting point of the gel is the temperature at which the ball begins to sink through the sample. The apparatus for facilitating these measurements is available, for example, a Physica AMV200 revolving ball viscometer from Anton Paar KG. A reversible gel also has a transition temperature at which, with a slow increase in temperature, all ordering, whether of microscopic or macroscopic limit, has completely disappeared. This transition temperature (from order to disorder) can be measured by differential scanning calorimetry (DSC). The transition temperature of a reversible gel, measured by DSC; it usually coincides approximately with the fusion of the gel, and can be observed visually. Although xanthan gum can be incorporated as a thickener into aqueous compositions containing surfactant, the resulting products tend to have a yarn-forming texture and a slimy feel. It has been found that gels formed by the cooling of a variety of polymers of biological origin are incompatible with the formation of foam surfactant. The surfactant makes the gel unstable and the separation phase occurs with cooling or with subsequent storage. EP-A-355908 teaches that polysaccharides capable of forming a reversible gel can be used to form flowable, mobile, viscous compositions by subjecting the composition to shear while forming takes place. The resulting compositions can be called "sheared gel". This document exemplifies a variety of products, one of which is called "cleansing gel" and includes a low foaming nonionic surfactant as an emulsifier. It has been found that it is possible to form detergent compositions which are shear gels and include foam surfactant. According to the present invention, there is provided an aqueous detergent composition, having the form of a thickened fluid, containing a foam surfactant and a polymer or polymer mixture capable of forming a reversible gel in water, the polymer is present in the composition as a multiplicity of separate gel particles. In the present specification, the term "thickened fluid" is used to denote a composition with a viscosity greater than that of water. In order for the gel particles to remain stable with the presence of the surfactant, it will generally be desirable that the polymer or polymer mixture does not require polyvalent cations in order to form the precursor aggregates which are subsequently capable of achieving an intermolecular association, the which would lead to a gel crosslinking. Accordingly, it is desirable that the polymer or mixture be capable of forming a reversible gel when dissolved in a sufficient concentration in distilled or demineralized hot water and allowed to cool to an ambient temperature of 20 ° C. The composition may consist solely of a continuous aqueous phase and of the gel particles therein. However, compositions thickened with gel particles, in accordance with this invention, have been found to be very effective in suspending other materials, and therefore, a composition of this invention can incorporate particles suspended from a liquid immiscible with water ( example, an oil immiscible with water) or a solid other than a gel polymer. The amount of these particles may be within the range of 0.1 to 40% by weight, preferably 0.1 to 25% by weight and more preferably 0.5 to 20% or by weight of the composition. The compositions incorporating this invention can be made with viscosities of a wide range. At one extreme, the compositions can be freely mobile, self-leveling and pourable, although denser than water. On the other hand, they can be made as viscous liquids that can be squeezed out of a deformable container and even more so that they are too viscous to spill, but very slowly. They are thinned by shearing, which represents a useful property, especially in the compositions for personal washing, because the user can perceive the product very thick and viscous, but easy to apply. An advantage of viscous shear gels, compared to compositions thickened in some other form, is that they are better for retaining the form in which they have been squeezed for ejection. If the compositions are heated to a temperature above the melting and transition temperatures, the individual gel particles will fuse and will not reform as separate particles upon cooling, but will not be a problem during everyday use, since the reversible gels, usually They have melting temperatures above normal room temperatures. The viscosity of the compositions incorporating this invention can be measured using the same techniques that are used to measure the viscosities of other thickened liquid compositions. One suitable apparatus is the Haake Rotoviscometer, another is the Carri-Med CSL 500 viscometer. Many of the compositions of this invention will have a viscosity within the range of 0.1 Pa.s to 100,000 Pa.s at a shear rate of 10 sec. "1, measured at 20 ° C, more preferably a viscosity within the range of 0.1 Pa.s to 20,000 Pa.s at a shear rate of 10 sec. "1, and more preferably a viscosity within the range of 0.1 Pa.s to 10,000 Pa.s at a ratio 10 sec shear "1, measured at 20 ° C, preferably superlative a viscosity within the range of 0.1 Pa.sa 1, 000 Pa.s at a shear rate of 10 sec "1, measured at 20 ° C. A route for the preparation of sheared gel particles required for this invention begins with the provision of an aqueous solution of the polymer or polymer mixture. , at a temperature above the melting temperature of the gel (and probably also over its order-to-disorder transition temperature), then cooling the solution to a temperature below the setting temperature of the gel, while applying shear to the In general, the solution will be subjected to shear while it is cooled to 60 ° C or about 25 ° C or less.On a small scale, this can be carried out in a beaker with a mechanical stirrer in the beaker, providing a vigorous stirring while cooling the contents of the beaker is allowed.We prefer to carry out the preparation using a heat exchanger with scraping surface, which can be star equipped conveniently, to operate under a partial vacuum, to reduce the incorporation of air bubbles within the composition as the formation of the gel takes place. Another possibility for preparing the gel particles is to form a volume amount of the gel and then break it into small particles, for example by pumping it through a homogenizer. The gel particles, typically, will be of a size that can be observed under the microscope. Usually the average particle size will be within the range of 0.1 to 250 μm, and frequently, most of the particles will be between particle sizes of 0.1 to 300 μm. Preferably, the average particle size is between 0.5 or 1 μm and 200 μm can be in a range of 10 μm to 200 μm. An advantage of gel particles having this particle size, especially in the context of cleaning compositions, is that small polymer particles can improve cleaning by mechanically breaking the powder off the surface to be cleaned. This is particularly effective for topical compositions used for makeup removal. Generally, it will be desirable to form the gel particles by cooling the aqueous solution of the gel-forming polymer or the polymer mixture in the substantial absence of a surfactant and then adding the surfactant subsequently. An alternative attempt is to incorporate the surfactant into the aqueous composition before the step of cooling it under shear. This is not possible for all gel-forming polymers. We have found that for many polymers, gel formation is inhibited by the presence of the surfactant, and even then the gel particles that have already formed remain stable if the surfactant is subsequently added. Thus, in a second aspect, this invention provides a method for preparing a detergent composition as set forth above, which comprises an aqueous, mobile, hot solution of the polymer or polymer mixture, cooling the solution through its gel temperature, subjecting it to shear during or after cooling and incorporating a foaming surfactant possibly before, but preferably after cooling it through the gel temperature. A laboratory scale mixing vessel with a scraping surface, which has been used successfully, is the TK Agi Homo mixer marketed by Tokoshu Kika Kogyo Co. Ltd, Japan. Heat exchangers and scraped surface homogenizers are used in the commercial production of margarine and other spreads and these apparatuses can be used to produce the compositions of this invention on a larger scale. A discussion on heat exchangers is given in Hárród in Journal of Food Process Engineering 9 (1986) pages 1-62. Among the suppliers of these devices are Armfield Ltd, Ringwood, Hampshire, England, Contherm Corporation, which is a division of the Alfa Laval Group, USA Projects and APV (Crepaco) Ltd, Crawley, West Sussex, England. After formation of the gel particles, the addition of a foaming surfactant or other ingredients may be carried out, probably as liquid concentrates, but optionally as a solid surfactant or a fused and / or solid acid surfactant precursor, using a conventional mixing apparatus, operating with a low shear. Possibly a heat exchanger with scraping surface used to form the gel particles can also be used for a subsequent mixing operation, especially if it runs slower to provide a smaller shear. A mixing operation should not be allowed to heat the composition enough to cause the melting of the gel particles. If required, a composition with particulate content should be cooled before and / or during any subsequent mixing operation. In a highly preferred embodiment, the compositions according to the invention may comprise relatively high levels of polyol materials, since it has been found that the polyols impart some benefits to the compositions. These may include benefits in terms of processing, but also benefits in the resulting topical compositions. Materials and methods useful for this invention will now be described in more detail, by way of example only, with reference to the accompanying drawings, in which: Figure 1 is a cross section of a mixer useful for preparing gel particles in cut on a load basis; Figure 2 illustrates in diagram form the apparatus for continuous preparation; Figure 3 illustrates in diagram form another form of the apparatus used in Example 10; and Figure 4 illustrates in diagram form another form of the apparatus used in Example 12. The apparatus shown in Figure 1 is a homo-mixer TK Agi. It has a container 10 for contents with separate internal and external walls to allow a refrigerant to circulate through the space between them. The container has an upper lock 12. A rotor 14 inside the container extends through the upper lock 12 and is connected to a drive motor 16. The rotor 14 surrounds a stationary central stator 18. The deflectors 20, 22 project from the rotor and the stator, respectively. When the rotor pours the liquid into the container 10, it is sheared by the movement of the rotor 14 and its deflectors 20 relative to the stator 18 and its deflectors 22. In addition, the hinges 24 made of polytetrafluoroethylene projecting from the rotor 14 scrape the internal wall of the container 10. The upper lock 12 includes a provision in the 26 for connection with a vacuum pump. Gas tight seals are provided between the rotor 14 and the upper lock 12. Accordingly, the vacuum can be applied inside the container 10 through the connection 26. In order to prepare a composition according to the invention using this apparatus, an aqueous solution of the polymer, heated on the container, is placed in the container. its gel temperature. Then, the upper lock 12 is placed in the container and the contents of the container are cooled by circulation of the refrigerant through the space between the walls of the container. At the same time, the rotor is turned over and the vacuum is applied to the connection 26, so that cooling of the contents of the container under shear conditions is carried out in this way, while suction through the air outlet 26 prevents the formation of gel bubbles. Accordingly, as the content cools below its gel temperature, a multiplicity of small gel particles are formed. Once the contents of the container have cooled below their gel temperature and these particles have formed, the surfactant can be mixed with the contents of the container either by removing the top lock and adding a liquid concentrate (or optionally a solid surfactant or a solid and / or fused acid precursor) of the surfactant to the container 10, or by transferring the contents of the container 10 and also of the surfactant to a separate mixer.
Figure 2 illustrates a preferred form of the apparatus comprising several independent pieces of equipment connected together by a pipe structure. A hot aqueous solution of the polymer is prepared and maintained in a supply container T1. It is supplied by it by means of a pump P1 suitable to a heat exchanger with scraping surface A1, which is in the form of a cylinder for the through flow of the polymer solution and which is surrounded by a chamfering for the coolant. Within this heat exchanger is located a large diameter arrow with scraper blades having springs to hold them against the inner surface of the cylindrical wall of the container. The rotation of the central shaft by a motor applies shear to the polymer solution as it passes through the heat exchanger A1. As the polymer solution passes through the heat exchanger A1, it cools below its gel temperature under shear conditions and this leads to the formation of gel particles in a continuous aqueous phase. The resulting composition passes from the heat exchanger A1 to a second heat exchanger A2 which is similar, with the exception that it operates at a lower speed. This is used to cool the composition one more time. The composition then flows to a mixer C, which, like the units A1 and A2, perform the functions of heat exchange. However, within unit C there are stationary baffles projecting inward from the walls of the heat exchanger and a small, central diameter arrow driven by a motor, which carries other deflectors projecting between the stationary deflectors of the cylinder wall. There are no scrapers in this device. Here, the composition is mixed with a surfactant solution supplied from the supply container T2 by a suitable pump P2. The mixture leaving the high-speed mixer C is a composition according to the present invention. It may be convenient to cool it by passage through another heat exchanger with scraping surface A3 operating at low speed before the composition is supplied as a finished product or packaged in containers. Pumps P 1 and P 2 may be provided, conveniently, as separate channels of a ratio piston pump, which is a convenient way to ensure constant proportions are supplied from each of the tanks T 1, T2. The mixing apparatus, pumps and heat exchangers with scraping surface used in the apparatus as above, may be of the types commonly used for the production of margarine and other spreads. Another name for the heat exchanger with scraping surface that provides the through flow of the material is a "voter". These parts of the apparatus can be manufactured in a variety of sizes ranging from small units that can be adjusted in a laboratory table to a large-scale production plant. Manufacturers of these devices include Armfield Ltd, Cantherm Corporation and APV Projects (Crepaco) Ltd, mentioned above. There are two generally preferred processes for preparing the sprayed gel compositions according to the inventions using the equipment described above. In the first, the water, the polymer and optionally a polyol compound are added to a main mixing vessel (with or without a static homogenizer) and heated under vacuum to 90 ° C. The mixture can then be cooled, under vacuum When using a high speed wall scraper, quickly at 50 ° C and then more slowly at 20 ° C. The composition may then be subjected to a static homogenizer while, if required, it is warmed to 40 ° C, while at the same time a surfactant or an acid form of the surfactant is added to the top of the mixture. Alternatively, the surfactant can be added by dripping the fused surfactant through the contents of the funnel, which preferably is under vacuum, at high level from the scraper of the wall and / or the homogenizer. After this, the acid form of the surfactant can be neutralized with alkali (as TEA or KOH) can be added as required slowly through the funnel, with continuous high level from the wall scraper and / or homogenizer. Additional ingredients can be added at this stage (including any surfactant material that can be added by coextrusion or injection), and then the composition can be cooled to room temperature and the perfume and preservatives added. The pH is checked and adjusted and finally any suspended particles that are required, optionally, are added while the composition is subjected to vacuum and low shear only from the wall scraper, before discharging the composition. Alternatively, in place of the above steps, prior to initial cooling at 20 ° C, a rotating micro line can be used to shear the water, the polymer and optional polyol mixture, and subsequently cool the mixture from 90 ° C to 20 ° C. ° C. The resulting polymer sheared gel can be processed after compliance with the remaining steps above.Types of Polymer The compositions of this invention contain a polymer or a polymer mixture capable of forming a reversible gel. It is desirable that the polymer be capable of forming a gel without requiring the presence of metal salts. (Polymers that require the presence of ionic species as a prerequisite for gel formation are apt to be destabilized by a surfactant even if they are formed as sheared gel particles). Generally, this means that this polymer, dissolved in demineralized water at a certain concentration between 0.1 and 10% by weight, will form a gel upon cooling the solution without stirring at an elevated temperature of 90 ° C to 20 ° C for 24 hours. In this gel formation test, the polymer may or may not form a gel at any concentration within the range of 1 to 10% by weight. With some polymers it may be necessary to use more than 1%. With other polymers, concentrations as high as 10% by weight may not be adequate. Some polymers can form gels without remaining for more than 24 hours. The polymer or polymer mixture that is capable of forming a reversible gel will usually be of natural origin and preferably, one or more specific polysaccharides will be used. However, it is possible for the polymer or one or more polymers in a polymer mixture to be a chemically modified natural polymer such as a polysaccharide which has been chemically treated to provide or alter the groups that constitute it. It is also possible that the polymer blend contains a synthetic polymer together with a natural polymer. However, usually, the polymer that is used will include a polysaccharide chain of natural origin. A polysaccharide that can be used is agar, which of course is well known to be used as a growth medium for microorganisms in vitro. Agarose is a linear polysaccharide, made basically of β-1,3 galactose residues alternating with a-1,4 galactose residues. The latter present as the 3.6 anhydride and are the L-enantiomer.
In the same way, agaropectin has residues of β-1,3 galactose alternating with a-1,4 residues of galactose, but includes sulfate, pyruvate and / or glucuronic acid residues. The term "agar" embraces a family of polymers containing agarose and / or agaropectin, ie polymers with a basic structure with alternating content of residues of 1-3-D-galactose and 1,4-L-galactose. The agar is extracted from certain species of red seaweed, mainly found in Japan. A description of agar is provided by Tetsujiro Matsuhashi in Chapter 1 in "Food Gels" edited by Peter Harris, Elsevier, 1990. Another category of polysaccharide that can be used is kappa carrageenan. Carrageenins are a class of polysaccharides that occur in some species of red seaweed. They are linear polysaccharides made from residues of β-1,3 and bound 1,4-galactose. The bound 1,4 residues are the D-enantiomers and sometimes occur as the 3,6-anhydride. Many of the galactose residues are sulfated. A variety of carrageenan structures have been described and commercial materials that approximate the ideal structures are available. However, the variations between these structures are presented, depending on the source of the carrageenan and the treatment that it suffers after its extraction. A description of the different types of carrageenan is provided in "Carrageenans" by Norman F Stanley, Chapter 3 of "Food Gels" mentioned above. Kappa carrageenan is sulphated in bound 1,3 galactose residues, but not in bound 1,4 residues. Iota carrageenan is sulfated in both residues. The lambda carrageenan has two sulfate groups in the 1,4-linked residues and a sulfate group in 70% of the 1,3 linked residues. Other types of carrageenan can be used in mixtures with kappa. There are the aqueous solutions of iota carrageenan as reversible gels, but these seem to be self healing. The iota carrageenan can be used to form the compositions according to this invention, but the compositions can become earthy during storage due to the self-healing property of the iota carrageenan gels and therefore, for this invention it is desirable to use kappa carrageenan or mixtures of kappa and iota. Lambda carrageenan in its own aqueous solution does not form gels because its higher charge density inhibits the association between the molecules and the consequent structuring in the liquids. However, some lambda carrageenan can be included in the mixtures with kappa, or it can be present as an impurity in the commercial products of kappa or iota carrageenin. If lambda carrageenan is included within a carrageenan mixture, the mixture may contain a majority (more than one medium of polysaccharide) of kappa or kappa and iota carrageenan with a lower proportion of lambda carrageenan. Another polymer that can be used is furcellaran. The furcellaran is similar to kappa carrageenan, but is only partially sulfated in the bound 1,3-galactose residues. A polymer of bactericidal origin that can be used is gelan. It is the polymer of a tetrasaccharide repeating unit, containing glucose, glucuronic acid and rhamnose residues.
There is some substitution with the acyl groups, but frequently these are removed during production to give a low acyl gelatin. The gelanes are the subject of Chapter 6 in "Food Gels", by G R Saunderson. Another possibility is to use the so-called synergistic gel that is based on the interaction of two types of polymers. In general, these can be formed of a polysaccharide which is a glucomannan with residues of mannose residues in its polymer chain, such as locust bean gum or guar gum and a second polymer which is xanthan or carrageenan. It is possible to include an additional thickener, such as a small concentration of xanthan gum, or curdlan in the composition in addition to the gel particles. This can possibly be added after the gel particles have been formed along with the surfactant. A composition in accordance with this invention will generally contain from 0.1 to 10% by weight of a polymer of natural origin. Normally, at least one half of the weight of this polymer will be one or more polymers capable of forming a reversible gel upon cooling from an elevated temperature at 20 ° C as a working solution such as demineralized water. The polymer capable of forming a reversible gel can constitute from 0.5 to 10% by weight of the complete composition, frequently from 0.2 to 0.5% by weight up to 5 or 8% by weight. In general, the viscosity of a sheared gel composition according to this invention will increase with the concentration of the polymer contained therein. The viscosity will also be affected by the size and shape of the gel particles, which in turn are affected by the conditions used to apply the shear during cooling.
In general, combinations of different cooling rates and different rotor speeds during shearing allow the optimization of the dispersion softness of the particles, suspension properties and viscosity, possibly because the shapes of the gel particles can vary between spherical shapes and filamentous.
Non-Surfactant Electrolyte Although it is generally desirable that the polymer be capable of forming a gel without the participation of ionic species, however, some polymers that are capable of forming a gel in distilled or demineralized water form gels of higher viscosity if certain amount of electrolyte. Notably, the viscosity of kappa carrageenan gel dispersions is increased by the presence of potassium ions and the viscosity of agar gel dispersions increases in the presence of calcium ions. Accordingly, a polymer solution that is cooled under shear to form gel particles as required for this invention, can include electrolyte to improve the strength of the resulting gel particles. The amount of electrolyte required may be a low percentage of the product, for example, 1%.
Foaming Surfactant The compositions of this invention contain at least 3% by weight of a foaming surfactant system, preferably from 5% by weight to 30% by weight. At least half and better at least two-thirds of the surfactant present is preferably selected from anionic, amphoteric or two-ionic surfactants, or alkyl polyglycosides or alkyl polyhydroxyamides (eg alkyl glucamides) which are non-ionic surfactants. Preferably, the composition contains at least 5% of an anionic surfactant, possibly accompanied by an amphoteric or two-ionic surfactant. Conveniently, the composition comprises 5 to 25% by weight of an anionic surfactant, preferably 5-15% of anionic surfactant. Ethoxylated alcohols, which are low foaming nonionic surfactants, may be present in an amount less than half the surfactant present. Preferably, an amount (if any) of such a surfactant is not greater than a quarter of the surfactant present. Another type of anionic surfactant which is frequently used in personal wash compositions and which may be used in the compositions of this invention is the alkyl ether sulfate of the formula: R 4 O (CH 2 CH 2 O) t SO 3 M wherein R 4 is the alkyl or alkenyl 8 to 18 carbon atoms, especially of 11 to 15 carbon atoms, t is an average value of at least 2.0 and M is a solubilizing cation such as sodium, potassium, ammonia or substituted ammonia. Preferably t has an average value of 3 or more. Other anionic surfactants can be used. Possibilities include alkyl sulfates, glyceryl ether, sulfosuccinates, taurates, sarcosinates, acyl isethionates, sulphoacetates, alkyl phosphates, acyl amino carboxylates, acyl lactates and soap. In some embodiments, carboxylate acyl amino surfactants are particularly preferred. Sulfosuccinates can be monoalkylsulfosuccinates with the formula: R5O2CCH2CH (SO3M) CO2M; and amido-MEA sulfosuccinates of the formula: R5CONHCH2CH2O2CCH2CH (SO3M) CO2M; wherein R 5 ranges from C 8 -C 20 alkyls, preferably, C 2 -C 15 alkyls and M is a solubilizing cation (as described above). Sarcosinates generally have the formula R5CON (CH3) CH2CO2M, wherein R5 varies from C8-C20 alkyls, preferably C ?2-C ?5 alkyls, and M is a solubilizing cation (as described above). Taurates are generally identified by the formula: R5CONR6CH2CH2SO3M, wherein R5 varies from C8-C20 alkyls, preferably C ?2-C ?5 alkyls, R6 varies from C1-C4 alkyls and M is a solubilizing cation (as described before). The acyl fatty isethionates have the formula: R-CO2-CH2CH2-SO3M wherein R is an alkyl group of 7 to 21 carbon atoms and M is a solubilizing cation as described above. Another class of foaming anionic surfactants are the long chain alkyl carboxylates and the alkyl ether carboxylates of the general formula: R- (OCH2-CH2) a-COOM wherein M is a monovalent alkali cation such as Na and / or K, or an organic cation such as ammonia, monoethanolammonium or triethanolammonium, a is an integer from 0 to about 7 and R is a straight or branched chain hydrocarbon group, saturated or unsaturated with about 10 to about 20 carbon atoms. Another class of suitable anionic surfactants are monoalkyl phosphate and dialkyl phosphate surfactants, such as for example dioctyl phosphate as well as carboxylate ether and ethoxylated citrate surfactants. The anionic detergent included in the composition will generally be selected to avoid a harsh detergent such as primary alkane sulphonate or benzene alkyl sulfonate. The amount, if any, of these is preferably less than 3% of the detergents present. An anionic surfactant can be used for use in conjunction with an amphoteric / two-ionic surfactant, namely betaine or sulfobetaine. The amphoteric / two-ionic surfactants for use in this invention are usually accommodated in the total structure formula R [- CONHÍCI-,) _ x _ y Where R1 is an alkyl or alkenyl of 7 to 18 carbon atoms; R2 and R3 are each independently alkyl, hydroxyalkyl or carboxyalkyl of 1 to 3 carbon atoms, m is 2 to 4 n is 0 or 1 X is alkylene of 1 to 3 carbon atoms optionally substituted with hydroxyl; and Y is -CO2 or -SO3. Suitable amphoteric / two-ion detergents within the above general formula include simple betaines of the formula: R ' R1 N CH CO R and amido betaines of the formula: R2 R 1 - CONH (CH,) - N m - CH CO.
R wherein m is 2 or 3. In both formulas R1, R2 and R3 are as defined above. R1 can be, in particular, a mixture of C2 and C14 alkyl groups derived from coconut so that at least half, preferably at least three quarters of the groups R1 have from 10 to 14 carbon atoms. R2 and R3 are preferably methyl. Another possibility is that the two-ion detergent is a sulfobetaine of one of the formulas: (CH,) SO ¿'3 where m is 2 or 3, or the variants of these in which (CH2) 3SO3 is replaced by -CH2 CHCH 2 S03 Another class of amphoteric surfactants are the alkylamino alkylamides, especially the amphoacetates of the general formula: RCO - NH - Cr ^ - CH 2 - N - CH 2 - COOIV C 2 H OH wherein M is Na, K, ammonia or triethanolammonium, and R is a saturated or unsaturated, straight or branched chain alkyl group with about 10 to 20 atoms.
The glucoside surfactants are non-ionic in nature and, of course, include glucoside residues. Suitable ones belong to the general formula: RO (R'O) t (G) x or RCO2 - (R'O) t (G) x where G is a pentose or hexose residue, R'O is an alkoxy group, x is at least one unit and R is an organic hydrophobic group of 6 to 20 carbon atoms, which is preferably aliphatic, whether saturated or unsaturated, branched, or notoriously straight, alkyl, alkenyl, hydroxyalkyl or hydroxyalkenyl. Particularly, R can be an alkyl or alkenyl of 7 to 14 or 16 carbon atoms. The value of t in the above general formulas is preferably zero, so that the unit - (R'O) t - of the general formulas is absent. In that case, the general formulas become: RO (G) x or RCO2 - (G)? If t is not zero, it is preferred that R'O is a residue of ethylene oxide. Other possibilities are residues of propylene oxide and glycerol residues. If the parameter t is not zero for R'O to be present, the value of t (which can be an average value), will preferably be within the range of 0.5 to 10. The G group is typically derived from fructose, glucose , mannose, galactose, talose, gulose, allose, altrosa, idosa, arabinose, xylose, lixose and / or ribose. Preferably, G is provided essentially exclusively by the glucose units. The intersaccharide bonds can be from position-1 to 2, 3, 4 or position-6 of the attached saccharide. The hydroxyl groups in the sugar residues can be substituted, for example, etherified with short alkyl chains, of 1 to 4 carbon atoms. Preferably, a sugar residue carries no more than one substitute of this kind. The value x, which is an average, is generally called the degree of polymerization. Desirably, x varies between 1 and 8. The values of x can be between 1 and 3, especially 1 and 1.8. The alkyl polyglycosides of the formula RO (G) x ', that is, a formula such as those mentioned above in which t is zero, are available from Horizon Chemical Company, BASF and Henkel. The O-alkanoyl glucosides of the formula RCO2 - (G) x are described in International Patent Application WO 88/10147 (Novo Industri A / S). In particular, the surfactants described therein are glucose esters with an acyl group attached in the 3- or 6- position such as 3-O-acyl-D-glucose or 6-O-acyl-D-glucose. The 6-O-alkanoyl glucosides can be observed wherein the alkanoyl group incorporates an alkyl or alkenyl group with 7 to 13 carbon atoms. The glucose residue can be alkylated at its 1-position with an alkyl group having 1 to 4 carbon atoms, such as ethyl or isopropyl. Alkylation at position 1 allows these compounds to be prepared by regiospecific enzymatic synthesis as described by Bjorkling et.al. (J. Chem. Soc, Chem. Commun. 1989, p934).
The aldobionamides are amides of an aldobionic acid or aldobionolactone. The aldobionic acids are disaccharides or polysaccharide, in which the aldheido group (generally found in C1 position of sugar) have been replaced by a carboxylic acid. When drying, they are recycled to be aldobionolactones. The disaccharide can, in particular, be lactose or maltose, so that the aldobionamide is a lactobionamide or maitobionamide. More information about aldobionamides and their preparation can be found in EP-A-550278. The descriptions of amides of polyhydroxyalkyl fatty acids are found in US 2965576, EP 220676, EP 550557 and the documents referred to therein. The polyethylene oxide polypropylene oxide copolymers are for sale, for example, under the brand name Pluronic. The foaming properties of surfactants can be evaluated by a test that is carried out using a panel of advisors. An appropriate number of advisors to form the panel is 20. Each panelist uses surgeon's gloves, turned inside out, which are first washed with soap to remove the powder or talc from their surface, and then dried. The test solutions are prepared with a content of 2% by weight of surfactant in demineralized water. To carry out each test, 2.5 ml of the test solution is dosed slowly with a syringe directly into the dry gloves. Afterwards, the panelist rubs their hands together during and after dosing the surfactant solution on their hands and generate a mass. The panelist should be careful not to let go of the solution from his hands. The panelist continues to generate mass by rubbing his hands together for a period of approximately 10 to 20 seconds until the mass volume is perceived as constant, then the panelist measures the mass of the gloves by dipping his hands in a container of water while a collector funnel calibrated on them is maintained so that the mass is poured from the hands into the collector funnel. The results obtained from each panelist are averaged. A surfactant can be designated as a foam surfactant if the volume of foam obtained is greater than 10 cm 3. An alternative definition is to establish that the volume of foam for a foam surfactant should be at least half the volume generated from the same volume of an equivalent concentration solution of sodium lauryl ether sulfate with an average content of 3 ethylene oxide residues. . Some surfactants were tested in accordance with the above procedure and the following results were obtained: Brij 58, supplied by ICI, is an ethoxylated C16 fatty alcohol with an average of 20 ethylene oxide residues (C? 6E20). Genoprol ZRO, supplied by Hoechst, is sodium lauryl ether sulfate with an average of 3 ethylene oxide residues (SLES). Dehyton K, supplied by Henkel, is coconut amidopropyl betaine (CAPB). Plantaren 2000 UP, supplied by Henkel, is a polyalkyl glucoside in which the alkyl chain has an average of 10 carbon atoms and the molecules contain an average of 1.4 glucoside residues. Jordapon Cl, supplied by PPG Mazer, is sodium cocoyl isethionate (SCI). In a preferred embodiment, the composition contains relatively high levels of polyol materials. Typically, the polyol compounds can be present at a level of up to 90% by weight, more typically 2-60% by weight, preferably 5-50% or by weight and more preferably 10-45% by weight of the composition. Suitable polyol materials include glycerol, sorbitol, hexanetriol, propan-1,2-diol, 1,3-butylene glycol, hexylene glycol and propylene glycol, as well as polyethylene glycols and polypropylene glycols. Suitable polyethylene and polypropylene glycols typically have a molecular weight within the region of 100-4000, preferably 200-2000. A preferred polyol material is glycerol. It has been found that the inclusion of a polyol material in the compositions according to the invention, provides a variety of benefits. First, compositions according to the invention containing relatively high levels of polyols have been found to have improved stability when subjected to a freeze / melt stability test. In addition, compositions containing high levels of polyols have been found to have a relatively good integration, in particular in terms of their viscosity and their ability to suspend particles. "The compositions containing polyols may also have improved clarity, in particular because the need to provide a more direct structuring of the product is reduced (for example by using slurries or carbomer polymers.) The inclusion of high levels of polyols may also be facilitating inclusions and gelling of beneficial agents in the composition Also, the inclusion of high levels of polyol, together with the use of the polymer or polymer mixture can provide surprising improvements in the creaminess of foam stability of the dough In addition, the use of relatively high levels of polyols has been found to reduce the strength of the system with co-structuring (such as mud) with the polymer or the polymer mixture.Therefore, it has been found that these compositions have a reduced need of water in the system, since less water is required for hydration of the co-structuring, which in the practice, increases the options for an experienced person with respect to surfactant systems that can be used or accommodated in the composition. The use of high levels of polyols in the systems has also been found advantageous from a processing perspective, since as mentioned before in the application, it is desirable that the surfactants be added to the polymer mixture after it has been formed and cooled, to avoid phase separation. The addition of relatively high levels of polyols can result in the change of a phase boundary for the composition, which means that isotropic liquids of low viscosity can be formed. These are relatively easy to process compared to crystallized liquid phases of high viscosity (such as H1 or cubic) that would otherwise form under certain circumstances.
Other materials may be included than in the compositions of this invention. The possibilities include coloring agents, opacifying agents, organic polymers, perfumes, among which are perfumes deodorants, bactericidal agents to reduce the microflora in the skin, antioxidants and other preservatives.
The compositions according to the invention may optionally contain a beneficial agent. The beneficial agent can be an emollient oil, which refers to a substance that softens the skin (stratum corneum) directly or by increasing the water content and keeping it soft by delaying the decrease in water content. Suitable emollients and beneficial agents include: (a) silicone oils and gums and modifications thereof such as cyclic or linear polydimethylsiloxanes; amino, alkylaryl alkyl, and aryl silicone oils; (b) fats and oils, including natural fats and oils such as jojoba oil, soy, rice bran, avocado, almonds, olive, sesame, diopso, castor, coconut, mink; cocoa fat, beef tallow, lard, hardened oils obtained by the hydrogenation of the aforementioned oils, and mono, di and synthetic triglycerides such as glyceride of myristic acid, and glyceride of 2-ethylhexanoic acid; (c) waxes such as carnauba, spermaceti, beeswax, lanolin and derivatives thereof; (d) hydrophobic plant extracts; (e) hydrocarbons such as liquid paraffins, petrolatum, petrolatum, microcrystalline wax, ceresin, squalene, pristan and mineral oil; (f) higher fatty acids such as lauric, myristic, palmitic, stearic, behenic, oleic, linoleic, linolenic, lanolic, isostearic, and polyunsaturated fatty acids (PUFA); (g) higher alcohols such as lauric, cetyl, stearyl, oleyl, behenyl, cholesterol and 2-hexydecanol alcohol; (h) esters such as cetyl octanoate; myristic lactate, cetyl lactate, isopropyl myristate, myristyl myristus, isopropyl palmitate, isopropyl adipate, butyl stately, decyl oleate, cholesterol isostearate, glycerol monostearate, glycerol distearate, glycerol tristateate, alkyl lactate, alkyl citrate and alkyl tartrate; (i) essential oils such as mint, jasmine, camphor, white cedar, sour orange peel, ru, turpentine, cinnamon bergamot, citrus unshiu, aromatic calamus, pine, lavender, laurel, clove, hibiscus, eucalyptus, lemon, blossom star, thymus, pepper, rose, sage, menthol, cineraria, eugenol, citral, citronella, borneol, linalool, geraniol, enotera, camphor, thymol, espirantol, penena, limonena, and terpenoid oils; (j) lipids such as cholesterol, ceramides, sucrose esters and pseudo-ceramides as described in European Patent Specification No. 556,957; (k) vitamins such as vitamin A and E, and vitamin alkyl esters, including those alkyl esters of vitamin C; (I) sunscreens such as metioxyoctyl cinnamate (parsol MCX) and benzoylmethane butyl methoxy (Parsol 1789); (m) phospholipids; (n) antimicrobial agents; (o) hydroxy acids such as alpha and beta hydroxy acids; (p) cationic polymers for conditioning the skin or a beneficial agent for aid in the deposition of the skin; and (q) mixtures of any of the above components. A particularly preferred beneficial agent is silicone, preferably silica with a viscosity greater than about 50,000 centipoise. An example is polydimethylsiloxane with a viscosity of about 60,000 centivíscosidades. The beneficial agent can typically be present in the compositions according to the invention at a level of 0.1-20% by weight.
Example 1 Several compositions with a carrageenan content were prepared together with a surfactant. The carraginins that were used are established in the following table: Two surfactants were used: Sodium sulfate lauryl ether, average 3Eo, (SLES) and coconut amidopropyl betaine (CAPB) supplied by Goldschmidt as Tegobetaine CK. The surfactants were used in a constant ratio of 13 parts SLES to two CAPB parts. The general method of preparation was to dissolve the surfactants in demineralized water to make a concentrated solution (25% by weight of the surfactant) at 60-70 ° C. The polymer, in pulverized form, was dissolved in demineralized water at 90-100 ° C. The appropriate amounts of the two solutions were mixed to form a solution containing 10% by weight of the surfactant and a selected concentration of the polymer. Electrolyte was added to this solution. The mixed solution was placed in a container of a TK Agi Homo mixer as described above with reference to Figure 1. The mixer was started at 100 rpm, while the composition was cooled in the mixer from 75 ° C to 20 ° C. ° C for a period of 60 minutes. The compositions prepared are set forth in the following table.
The comparison of samples 1 to 5 illustrates a small but progressive increase in viscosity with kappa carrageenin up to 3% kappa. With an amount of 4.6% kappa, the system is rigid and paste-like, but even so it is easily distributed when rubbing (propan-1,2-diol was added to the base surfactant solution to allow higher concentrations to be used without the hexagonal formation phase). By increasing the concentration of KCl to 0.5% (sample 6), to increase the strength of the gel, it does not appear to result in a more viscous system. Samples 6 and 7, which contained some carrageenan iota, had properties similar to sample 2, but were a little more elastic as a consequence of their content of carrageenan iota. The effect of lambda (samples 9, 10 and 11) is to improve softness without greatly influencing the viscosity. An amount of sheared gel from sample 4 containing 3% kappa carrageenin was reheated to 70 ° C and then allowed to cool to room temperature without agitation. The result was a rigid gel, which indicated that the mobility of the composition formed under shear should be attributed to the transformations of the carrageenan solution in small gel particles during cooling.
Example 2 Samples 4, 8 and 10 of the previous example were packaged in 150 ml translucent polyethylene tubes with 1.5 mm diameter outlets. These samples were tested by 24 panelists who were instructed to observe the visual appearance and flow of the products in the tubes, then squeeze a certain amount of composition from the tube onto a transparent plastic sheet and make a visual observation of the product, feel the product with the tips of your fingers. Subsequently, they were asked to wash their forearms using each of the products. By way of comparison, the panelists were provided with a conventional bath gel in which the surfactant was thickened by the incorporation of salt. In general, the panelists commented that the products of this invention were less sticky or yarn forming than the control composition and that when removed from the tube the supplied material was less likely to settle by its own weight. (This observation can be attributed to the strong thinning character by shearing of the products of the invention). When used for washing, the products of the invention were perceived as a clean rinse, that is, it was observed that they left little or no residue or stickiness on the skin after drying.
Example 3 Agar sheared gels were prepared. The agar was "Deltagar LTS" from the Quest International plant in Kilnagleary, Carriglane, Co. Cork, Ireland. Xanthan was also used, supplied as "Keltrol F" by Kelco. The agar or mixture of agar and xanthan was dissolved in demineralized water and cooled from 75 ° C to 20 ° C. The polymer concentrations and the viscosities of the resulting compositions were: The compositions were studied under the microscope. The gel beads were observed, approximately the size indicated in the table. With 1% and 2% agar, it was observed that the pearls had small filaments projecting from them.
The inclusion of the small xanthan concentration led to the formation of slightly smaller beads with fewer filaments projecting from them. The composition was noticeably softer and less viscous. Compositions containing 2% to 4% agar were mixed with concentrated aqueous solutions of surfactant (25% by weight) in a proportion to give a composition with a content of 10% by weight of surfactant (13: 2 SLES: CAPB as in Example 1). The mixing was carried out in a beaker at 20 ° C using a paddle stirrer rotated by an upper motor at a low enough speed to avoid incorporation of bubbles.
Example 4: Bath Gel A bath gel was prepared in the following manner using the apparatus generally shown in Figure 2, but without an A3 heat exchanger. The agar, calcium chloride, potassium sorbate and sorbic acid were dissolved in hot water (>90 ° C) using a Silverson stirrer. The resulting hot agar solution (M) was transferred to tank T1 which was a 5 liter jacketed tank fitted with a lower stirrer, baffle and a tight sealing cap and was maintained at 95 ° C. It was stored in this tank for 30 minutes. one surfactant mixture by diluting two parts of a paste ether sulphate 70% active lauric (SLES) (Manro BES) with one part of propylene glycol to form a 46.7% active surfactant solution was prepared. To this solution was added 100% active cocoamide propyl betaine (Tegobataine CK) (CAPB) in an amount to reach a ratio of 13 parts SLES and 2 parts CAPB. Dyes, perfume and antioxidant were added as it was desired and the final surfactant solution (N) transferred to tank T2 which was one second tank jacketed 5-liter stirring maintained at 30 ° C. Aeration of the mixture was prevented by limiting the stirring speed to < 60 r.p.m. The compositions of the solutions (M) and (N) are set forth in the following table together with the compositions containing a total of 16% surfactant.
Tank T1 contained a non-demarcation micro-marker line as illustrated in Figure 2, connected to a P 1 channel of a piston supply pump and then to two heat exchangers A1 and A2 with scraping surface, each with a volume of approximately 15 ml arranged in series. The feed tank T2, jacketed, was connected to a second channel P2 of the supply pump and thence to one end of a C-shaped crystallizing mixer C of approximately 150 ml volume. The chalking temperatures of these units were controlled by glycol, hot or cold by circulation baths with suitable measures. Hot water (95 ° C) was pumped through the voter line to preheat the units and feed lines. The agar solution (M) was pumped through the line with the 100% pump set P1 until a sheared gel formed. This material was fed into the waste tank or reworked in the feed tank T1. Meanwhile, the solution (N) of surfactant was pumped (P2 adjusted to 47%) through mixer C with its stationary rotor. When it was filled, the rotor of mixer C was started and adjusted to 500 r.p.m. The sheared gel formed of the solution (M) was fed to a port located centrally in the barrel of the mixer C. The bath gel thus formed has a composition as set out in the following table under the heading "Product Composition". It was collected from the outlet of mixer C and packed in plastic bottles. The typical conditions of march are established in the following table: An essentially transparent, foaming, viscous and stable phase bath gel was produced, which exhibited an ability to form peaks (i.e., character to maintain its shape), upon being squeezed out of the bottle. The product exhibited an excellent non-forming behavior of thin threads during use and left a soft feeling on the skin, however not sticky when dried.
Example 5: Basis of the bath humectant A bath moistening gel was prepared in a manner similar to Example 4. The agar, sodium caseinate, potassium sorbate and sorbic acid were dissolved in hot water (> 90 ° C) using a Silverson shaker. The hot solution was maintained at 90 ° C in tank T1 for 30 minutes before use. An oil phase was dispersed in the agar solution using a homogenizer (Crepaco) to achieve an average oil drop size of approximately 1 miera in the resulting M emulsion. The foamy surfactant composition N (approximately 50% active) was placed in a separate tank and maintained at 30 ° C with slow agitation (<60 r.p.m.). The compositions of the M and N solutions are set forth in the following table, together with the composition of the product made therefrom, which contained a total of 10% surfactant. The oil droplets remained suspended in the composition of the product.
Solutions M and N were processed using the microvoting line and the procedure of Example 4. The running conditions are set out in the following table. The product was a bath gel, foamy, white, thick that exhibited good slimming flow properties but not yarn forming during its use. It left a feeling of soft and moist skin.
Example 6: Base of the bath moisturizer Example 5 was repeated but the emulsifier (sodium caseinate) was omitted. The product was a white, thick, stable gel. It was essentially non-foaming when it was initially applied to the skin, it behaved a lot like a cleansing cream but it formed significant amounts of foam when diluted with water during the normal washing action, leaving the skin soft and moist. The compositions of the M and N solutions and the product are established in the following table: Example 7: Base of the thick bath moisturizer Example 5 was repeated using a higher concentration of agar with the sodium caseinate replaced by gelatin (Bloom 150) and with the addition of calcium chloride for the M solution. The surfactant N solution remained unchanged. The compositions are established in the following table: The conditions of the voting line process were as established in the following table: Example 8: Base for shampoo for hair A preparation was prepared at very high viscosity and with a very high concentration of active surfactant, which contained a phase of cleansing surfactant for hair, with a typical foaming agent to allow dilution during further processing for shampoo for hair. As in Example 4, the agar was dissolved together with the potassium sorbate, sorbic acid and the calcium chloride in hot water (<90 ° C) using a Silverson mixer to form the agar M solution. A mixture of surfactant was prepared by diluting two parts of a slurry of 70% active lauryl ether (SLES) sodium sulfate (Manro BES) with one part of propylene glycol to form a 46.7% active surfactant solution. To this solution was added 100% active cocoamido propyl betaine (Tegobetaine CK) (CAPB) in an amount to achieve a ratio of 13 parts of SLES to two parts of CAPB. Antioxidant was added and the final solution (N) was transferred to a feed tank maintained at 30 ° C. Aeration of the mixture was prevented by limiting the stirring speed to < 60 r.p.m. The compositions of the M and N solutions and the high viscosity composition made therefrom, which contained 24% surfactant are set forth in the following table: The processing of the two solutions was carried out using the design of the micro-voting line and the method of Example 4. The process conditions of the process are established in the following table: Example 9: Carraqinin base surfactant gel A stable, foaming surfactant gel was prepared using mixed xanthan and carrageenan. The powders of xanthan (Keltrol F, Kelco International Ltd), powders of pure carrageenan iota (Genuvisco X-0908, Hercules) and pure kappa-carragginine (Genugel X-0909, Hercules) were mixed dry and then dissolved in hot deionized water (> 80 ° C) using a Silverson stirrer, to which were added potassium sorbate and sorbic acid. The hot solution (M) was transferred to a jacketed feed tank and maintained at 85 ° C. A surfactant mixture was prepared by diluting two parts of a slurry of 70% active sodium lauryl ether (SLES) (Manro BES) with one part of propylene glycol to form a 46.7% active surfactant solution. This solution was heated to 60 ° C and 100% active cocoamide propyl betaine (Tegobataine CK) (CAPB) was added in an amount to reach a ratio of 13 parts SLES and 2 parts CAPB. To this solution N was added the solution M of hot polymer in the feed tank and was processed through the micro-voting line comprising the feed tank, the supply pump and a sequence of three heat exchangers with surface of scraping designated A1, A2, A3. The compositions and process conditions are established in the following two tables: Example 10: Liquid soap The composition of the previous Example was processed in a different manner to produce a liquid soap product. The carrageenins, sorbic acid and potassium sorbate were dissolved in hot water (<80 ° C) with stirring as before to form the solution M, which was maintained at this temperature of the stirring tank. The xanthan was dispersed in deionized water, heated to 95 ° C and maintained at this temperature in a second stirred tank T2 (solution X). The surfactant solution (N) was prepared as in Example 6 and kept in a third tank T3 of agitation at 30 ° C. A micro-voter process line was used as illustrated in Figure 3. It was prepared in such a way that solution X was fed from tank T2 through one end of mixer C1 while solution M of carrageenan was fed from tank T1 to a port located centrally in the same mixer. The cooling and sheared gel formulation was carried out in the mixer. After passing through the heat exchanger A with scraping surface to complete the cooling, the mixture was supplied to a centrally located port of a second mixer C2 through which the solution N of tank T3 was already flowing. The processing conditions are established in the following table: Example 11: Liquid fabric washing base A foaming surfactant preparation was formulated which is intended for use in automatic fabric washing, it was prepared by using a micro-voting line of the type shown in Figure 2 and described in Example 4. Agar, calcium chloride, potassium sorbate and sorbic acid were dissolved in hot water (> 90 ° C) using a Sílverson shaker. The hot solution (M) was transferred to a jacketed T1 tank fitted with a lower stirrer, a baffle and a sealed sealing cap and kept at 95 ° C for 30 minutes. A surfactant mixture was prepared by diluting a slurry of sodium lauryl ether sulfate (SLES) (Manro BES) with propylene glycol and a mixture of ionic and nonionic surfactants. Dyes, perfumes and preservatives were added as desired and the resulting solution (N) with the composition shown in the following table was transferred to a feed tank T2 maintained at 30 ° C. Aeration of the mixture was prevented by limiting the stirring speed below 60 rpm. The process was as in Example 4. The composition of the product was in the form of an optically clear liquid capable of suspending particles of insoluble solids. It contained a total of 22.9% surfactant. The compositions and process conditions are established in the following two tables: Example 12: Foamy Cleaner This preparation was carried out using a microvoting line as shown in Figure 4. Gelan (Kelcogel F, Kelco) was dissolved in hot deionized water (> 90 ° C) using a Silverson mixer. and transferred to a stirred tank T1 and held at 90 ° C with slow agitation (solution M). A solution of calcium chloride was prepared in deionized water and transferred to a second tank T2. The N-mixture of surfactant of Example 4 was prepared and transferred to a third stirred tank T3. The micro-voting line had two feed tanks T1, T2 connected by separate channels P1, P2 of a supply pump to a Teepiece located at the entrance of a first heat exchanger A1 with scraping surface, followed in sequence by a mixer C1 and two other exchangers A2, A3. Finally, the output of the last exchanger A3 was connected to a centrally located port of a second mixer C2, which was supplied from the supply tank T3 through a channel P3 of a third pump. The three solutions (M, N and CaCI2) were processed through this line to form a pourable, stable product containing 16% > of surfactant, which formed good foam during use. The compositions and process conditions are established in the following two tables: EXAMPLE 13-26 - Foaming Cleaners The following compositions were prepared using a container with scraping wall surrounded by a water coating similar to that described in relation to Example 1, if necessary and optionally under vacuum, in particular the place where it is processed. the composition is relatively thick (for example, it has a relatively high agar concentration), or it is required in particular to avoid aeration. The processing conditions were generally the same as those described in relation to Example 1 1, wherein the agar, the water and the polyols (for example, glycerol, PEG 400, propan-1,2-diol) and ethanol were prepared as a previous solution, when mixed using a Silverson agitator before being transferred to the tanked T1 tank and kept at 95 ° C. The rest of the components, with the exception of perfume and preservatives, were formulated with the surfactants and processed as described with respect to Example 1 1.
In compositions 25 and 26, ethanol was added attached to the sheared gel. In some embodiments including relatively high short chain monohydric alcohols (e.g., greater than about 5%, or possibly greater than about 20%), such as ethanol, it is possible to process a sheared gel with the presence of an alcohol without surfactant, and then, to dose bound the surfactant to provide the final composition. This provides a way to prepare compositions containing relatively high levels of short-chain monohydric alcohols, compositions that may otherwise be relatively difficult to prepare. Some benefits associated with the aspects of the previous compositions were found. For example, it was found that compositions containing cocoyl potassium glycinate have good clarity and have a slimming property suitable for direct application, for example, on the face. Also, it was found that some of the compositions have the surfactant in an isotropic solution in a temperature range of 5-45 ° C, in which case the viscosity of the product is controlled only by the sheared gel particles. In these cases, the viscosity is not affected by the temperature, which facilitates the packaging of the product, making it suitable for distribution in tubes. Also, it was found that compositions comprising relatively substantial levels of polyols are tolerant to coextrusion or injection of a surfactant during the preparation and certainly considerably more than systems that are structured for example with mud or Carbopol (). It was also found that the incorporation of the polyols tends to affect the gelation rate and the mechanism, with the result that a relatively moderate shear rate could be used to generate the sheared gels and avoid the formation of hard gel agglomerates in parts. Not sheared from the mixer during cooling. The compositions containing the polyols also showed a tendency to suffer reduced levels of syneresis.
Examples 27-32 The following additional compositions were prepared for face washing. During the manufacturing method a thermostatically controlled wall heater was used, together with a scraping wall pallet. The container was evacuated to avoid trapped air. The vessel was loaded with water, polyol and agar to provide a pre-solution. This mixture was heated with stirring at 90 ° C. The resulting solution was then cooled to 50 ° C with rapid paddle mixing. The mixture was then cooled to 25 ° C with slow cooling and rapid paddle mixing to form a sheared gel. The solid surfactant was added to the sheared gel, which was dissolved by warming the composition to 40 ° C with gentle mixing. The composition was then cooled, perfumes, preservatives and clarifying agents were added and the composition was discharged.
The compositions contain relatively high levels of polyol materials.
Examples 33 to 40 represent other suitable compositions according to the invention.

Claims (14)

  1. CLAIMS 1. An aqueous detergent composition, which is in the form of a mobile, thickened fluid comprising a foaming detergent and a polyol material and a polymer or polymer mixture which is capable of forming a reversible gel, whose polymer or mixture of polymer is present in the composition as a multiplicity of individual gel particles with a particle size of less than 200 meters, wherein the polyol material is present in the composition at a level of 5 to 90% by weight and the polyol material is select from glycerol, sorbitol, hexanediol, propan-1,2-diol, 1,3-butylene glycol, propylene glycol, hexylene glycol, and polyethylene glycols and polypropylene glycols with molecular weights within the range of 100-4,000. 2. A composition according to claim 1, wherein the polyol material is present in the composition at a level of 5 to 50% by weight of the composition. 3. A composition according to claims 1 6 2, which detergent comprises a surfactant selected from anionic, amphoteric or two-ionic surfactants and contains at least 3% by weight of anionic surfactant, with a content of 5 to 25% ) of anionic surfactant. 4. A composition according to claims 1 to 3, which contains an anionic surfactant with a lower amount of two-surfactant. A composition according to Claims 1 to 4, wherein the foam surfactant contains non-ionic surfactant selected from alkyl glycosides, O-alkanoyl glycosides, polyethylene oxide polypropylene oxide copolymer copolymers, alkyl polyhydroxyamides, alkyl aldobionamides and mixtures thereof. 6. A composition according to any of the preceding Claims, wherein the polymer or polymer mixture comprises kappa carrageenan. 7. A composition according to any of the preceding Claims, wherein the polymer or polymer mixture comprises agar. 8. A composition according to any of the preceding Claims, which contains from 0.1 to 10% by weight of the polymer or polymer mixture. 9. A composition in accordance with any of the Prior claims, which include particles suspended from a liquid or a solid other than the polymer gel. A method for preparing a detergent composition according to any one of claims 1 to 9, comprising forming an aqueous, mobile, hot solution of the polymer or polymer mixture, cooling the composition to its gel temperature while which is subjected to shearing and incorporating a foaming surfactant before or after cooling. 11. A method according to Claim 10, wherein the surfactant is added to the solution after cooling to 35 ° C or less. 12. A method according to Claim 11, wherein the polymer or polymer mixture comprises kappa carraginin and the surfactant is present in the aqueous solution while cooling under shear. 13. A composition according to claim 9, wherein the suspended phase is selected from silicone oils or gums, triglyceride waxes or oils, mineral oil, petrolatum, polyethylene or mixtures thereof. 14. A composition according to Claim 9, wherein the suspended particle is a sunscreen. RESU MEN An aqueous detergent composition, which is in the form of a mobile, thick fluid, comprising a foam detergent and a polymer or polymer mixture, which is capable of forming a reversible gel, whose polymer or polymer mixture is present in the composition as a multiplicity of individual gel particles.
MXPA00009601A 1998-04-03 1999-03-22 Detergent compositions. MXPA00009601A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9807269.7A GB9807269D0 (en) 1998-04-03 1998-04-03 Detergent compositions
PCT/EP1999/001901 WO1999051716A1 (en) 1998-04-03 1999-03-22 Detergent compositions

Publications (1)

Publication Number Publication Date
MXPA00009601A true MXPA00009601A (en) 2002-08-06

Family

ID=10829868

Family Applications (1)

Application Number Title Priority Date Filing Date
MXPA00009601A MXPA00009601A (en) 1998-04-03 1999-03-22 Detergent compositions.

Country Status (21)

Country Link
US (1) US6329331B1 (en)
EP (1) EP1066366B1 (en)
JP (1) JP4625580B2 (en)
KR (1) KR100614161B1 (en)
CN (1) CN1230513C (en)
AR (1) AR014796A1 (en)
AU (1) AU749720B2 (en)
BR (1) BR9909395B1 (en)
CA (1) CA2324956C (en)
CZ (1) CZ302724B6 (en)
DE (1) DE69926872T2 (en)
ES (1) ES2247796T3 (en)
GB (1) GB9807269D0 (en)
HK (1) HK1038583A1 (en)
HU (1) HUP0102359A3 (en)
ID (1) ID26415A (en)
MX (1) MXPA00009601A (en)
MY (1) MY120177A (en)
PL (1) PL191306B1 (en)
RU (1) RU2217488C2 (en)
WO (1) WO1999051716A1 (en)

Families Citing this family (98)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9927901D0 (en) * 1999-11-25 2000-01-26 Unilever Plc Laundry product
FR2810542B1 (en) * 2000-06-23 2004-02-27 Oreal FOAMING COSMETIC CREAM
KR100347665B1 (en) * 2000-07-11 2002-08-07 주식회사 동산씨앤지 Clear shampoo composition containing capsules and method of making the same
GB0026473D0 (en) * 2000-10-30 2000-12-13 Unilever Plc Shear gel compositions
DE10127104A1 (en) 2001-06-02 2002-12-05 Wella Ag Hair treatment composition useful for imparting hold, stylability or shine to human hair comprises dimensionally stable solid gel particles in a fluid matrix
FR2825629A1 (en) * 2001-06-11 2002-12-13 Oreal Stable foaming liquid composition for topical application, e.g. as cleansing milk for the skin, scalp and/or hair, containing organized surfactant system as a lamellar gel phase in aqueous medium
US20040247767A1 (en) * 2001-08-10 2004-12-09 Fischer Peter Alfons Process for the preparation of an emulsion or dispersion with controlled shape of the dispersed phase
DE60223762T2 (en) 2001-08-10 2008-10-23 Unilever N.V. Composition containing dietary fibers
AR040093A1 (en) * 2002-05-21 2005-03-16 Procter & Gamble CLEANING COMPOSITION THAT INCLUDES SUSPENDED PEARLS
US20040097385A1 (en) * 2002-11-18 2004-05-20 Unilever Home & Personal Products Usa, Division Of Conopco, Inc. Viscoelastic cleansing gel with surfactant solutions containing polysaccharides and their derivatives polysaccharide hydrocolloids
US20040120915A1 (en) * 2002-12-19 2004-06-24 Kaiyuan Yang Multifunctional compositions for surface applications
US7875582B2 (en) * 2003-05-22 2011-01-25 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Nonbar personal product compositions comprising crystalline wax structured benefit agent premix or delivery vehicle
GB0311817D0 (en) * 2003-05-22 2003-06-25 Unilever Plc Particles for thickening food compositions
US7737100B2 (en) * 2003-05-23 2010-06-15 Transfer Technologies International Corporation Compositions and methods for preventing and treating corrosion of metal surfaces
US7737099B2 (en) * 2003-05-23 2010-06-15 Transfer Technologies International Corporation Compositions and methods for preventing and treating corrosion of metal surfaces
DE10342114B3 (en) * 2003-09-10 2005-04-07 Kraft Foods R & D, Inc. Process for the preparation of flowable concentrated suspension systems and suspension-based products prepared by this process
NZ551546A (en) 2004-05-07 2010-07-30 Deb Ip Ltd Foamed cleanser with suspended particles, a method of producing same, and a dispenser therefore
JP2006298916A (en) * 2005-03-25 2006-11-02 Lion Corp Hair cleanser composition
EP1874914B1 (en) 2005-04-21 2012-09-26 Colgate-Palmolive Company Liquid detergent composition
FR2904537B1 (en) * 2006-08-04 2013-04-12 Oreal COSMETIC COMPOSITION COMPRISING AT LEAST ONE LAMBDA CARRAGEHENAN TYPE POLYSACCHARIDE IN ASSOCIATION WITH AT LEAST ONE PARTICULAR POLYOL; PROCESS FOR COSMETIC TREATMENT OF KERATIN FIBERS AND USE OF THE COMPOSITION
US20080070823A1 (en) * 2006-09-15 2008-03-20 Philip Gorlin Liquid Detergent Composition
WO2008038798A1 (en) * 2006-09-29 2008-04-03 Mitsui Mining & Smelting Co., Ltd. Non-aqueous electrolyte secondary battery
WO2008055816A1 (en) * 2006-11-08 2008-05-15 Unilever Plc Conditioning shampoo compositions
CA2667555A1 (en) * 2006-11-08 2008-05-15 Unilever Plc Conditioning shampoo compositions
US20080128423A1 (en) * 2006-12-01 2008-06-05 Donald Rick Self-warming moisturizing lotion in a dual chamber bottle
US20080128426A1 (en) * 2006-12-01 2008-06-05 Donald Rick Self-warming sanitizing composition in a dual chamber bottle
US20080128425A1 (en) * 2006-12-01 2008-06-05 Donald Rick Self-warming analgesic composition in a dual chamber bottle
MY150444A (en) 2006-12-15 2014-01-30 Colgate Palmolive Co Liquid detergent composition
US20080242581A1 (en) * 2007-04-02 2008-10-02 Colgate-Palmolive Company Liquid Detergent With Refractive Particle
US7879780B2 (en) * 2008-09-23 2011-02-01 Conopco, Inc. Stable cleansing compositions containing fatty acyl isethionate surfactant products having more than 10 wt. % of fatty acid/fatty soap content using high level of polyol and methods thereof
CN102209576A (en) * 2008-11-07 2011-10-05 荷兰联合利华有限公司 Conditioning shampoo composition comprising an aqueous conditioning- gel
KR20110086555A (en) * 2008-11-07 2011-07-28 유니레버 엔.브이. Concentrated shampoo
AU2009312929A1 (en) * 2008-11-07 2010-05-14 Unilever Plc Conditioning shampoo comprising an aqueous conditioning gel phase in the form of vesicles
US20100215700A1 (en) * 2009-02-25 2010-08-26 Conopco, Inc., D/B/A Unilever Shear Gels and Compositions Comprising Shear Gels
CN102459554B (en) * 2009-06-08 2014-12-10 宝洁公司 Process for making a cleaning composition employing direct incorporation of concentrated surfactants
US20120093756A1 (en) * 2009-06-24 2012-04-19 Andrew Malcolm Murray Concentrated shampoo
DE102009028143A1 (en) 2009-07-31 2011-02-03 Evonik Stockhausen Gmbh Skin protection agents, in particular against hydrophobic (lipophilic) as well as against hydrophilic (lipophobic) pollutants
FR2954162B1 (en) * 2009-12-23 2012-03-09 Oreal COSMETIC COMPOSITION COMPRISING AT LEAST TWO GUMES OF CARRAGHENANES
WO2011111854A1 (en) 2010-03-12 2011-09-15 日清オイリオグループ株式会社 Composition for external use on skin, cosmetic, and cleaning agent
US9040031B2 (en) 2010-07-08 2015-05-26 Conopco, Inc. Hair care composition
US8668916B2 (en) 2010-09-24 2014-03-11 Conopco, Inc. HIPE-gelation process for making highly concentrated, spherical biopolymer gel particle suspensions
US8114826B1 (en) 2011-02-08 2012-02-14 Conopco, Inc. Concentrated soap based cleansing compositions
FR2983069B1 (en) 2011-11-25 2015-03-27 Oreal COSMETIC COMPOSITION CONTAINING AN ASSOCIATION OF A GELIFIABLE WATER SOLUBLE POLYSACCHARIDE, STARCH AND LOADS
JP6729925B2 (en) 2012-05-30 2020-07-29 クラリアント・ファイナンス・(ビーブイアイ)・リミテッド Composition containing N-methyl-N-acylglucamine
CN104540494B (en) 2012-05-30 2017-10-24 科莱恩金融(Bvi)有限公司 N methyl Ns acyl glucamides as solubilizer purposes
US9622951B2 (en) 2012-10-29 2017-04-18 The Procter & Gamble Company Personal care compositions
DE102012021647A1 (en) 2012-11-03 2014-05-08 Clariant International Ltd. Aqueous adjuvant compositions
EP2740467A1 (en) * 2012-12-10 2014-06-11 OTC GmbH Pumpable cosmetic composition with a high humectant content and foaming properties
WO2014149019A1 (en) * 2013-03-15 2014-09-25 Hercules Incorporated Composition and method of producing personal care compositions with improved deposition properties
JP6537494B2 (en) * 2013-04-20 2019-07-03 クラリアント・インターナシヨナル・リミテツド Composition comprising oily substance, fatty acid, amino acid surfactant, and N-methyl-N-acyl glucamine
CN103263873A (en) * 2013-04-25 2013-08-28 威莱(广州)日用品有限公司 Solubiliser composition and preparation method thereof
KR101305349B1 (en) * 2013-05-16 2013-09-06 (주) 제이티 Composition of hydrogel soap, hydrogel soap and preparing method thereof
DE102014005771A1 (en) 2014-04-23 2015-10-29 Clariant International Ltd. Use of aqueous drift-reducing compositions
FR3025101B1 (en) * 2014-08-28 2017-12-29 Oreal FOAMING COMPOSITION COMPRISING AT LEAST ONE SURFACTANT OF THE N-ACYLSARCOSINATE TYPE
CA3198374A1 (en) 2014-09-09 2016-03-17 Hydromer, Inc. Antimicrobial soaps containing carvacrol and methods of using same
MX369415B (en) 2015-04-23 2019-11-07 Procter & Gamble Concentrated personal cleansing compositions.
BR112017022021B1 (en) 2015-04-23 2021-07-06 The Procter & Gamble Company HAIR TREATMENT COMPOSITION
US10952950B2 (en) 2015-04-23 2021-03-23 The Procter And Gamble Company Concentrated personal cleansing compositions and methods
EP3285728B1 (en) 2015-04-23 2019-12-18 The Procter and Gamble Company Concentrated personal cleansing compositions and methods
CN107530245B (en) 2015-04-23 2021-05-04 宝洁公司 Concentrated personal cleansing compositions and uses
DE102015219651A1 (en) 2015-10-09 2017-04-13 Clariant International Ltd. Compositions containing sugar amine and fatty acid
DE202015008045U1 (en) 2015-10-09 2015-12-09 Clariant International Ltd. Universal pigment dispersions based on N-alkylglucamines
WO2017106403A1 (en) * 2015-12-15 2017-06-22 The Procter & Gamble Company Hair cleansing composition
JP6813586B2 (en) 2016-03-03 2021-01-13 ザ プロクター アンド ギャンブル カンパニーThe Procter & Gamble Company Aerosol dandruff prevention composition
WO2017165191A2 (en) 2016-03-23 2017-09-28 The Procter & Gamble Company Imaging method for determining stray fibers
DE102016207877A1 (en) 2016-05-09 2017-11-09 Clariant International Ltd Stabilizers for silicate paints
US10888505B2 (en) 2016-10-21 2021-01-12 The Procter And Gamble Company Dosage of foam for delivering consumer desired dosage volume, surfactant amount, and scalp health agent amount in an optimal formulation space
CN109715131B (en) 2016-10-21 2022-04-26 宝洁公司 Low viscosity hair care compositions
US11185486B2 (en) 2016-10-21 2021-11-30 The Procter And Gamble Company Personal cleansing compositions and methods
WO2018075749A1 (en) 2016-10-21 2018-04-26 The Procter & Gamble Company Skin cleansing compositions and methods
MX2019003107A (en) 2016-10-21 2019-09-13 Procter & Gamble Stable compact shampoo products with low viscosity and viscosity reducing agent.
CN109843382A (en) 2016-10-21 2019-06-04 宝洁公司 For providing the concentrated type shampoo foam of hair-care beneficial effect
US11141361B2 (en) 2016-10-21 2021-10-12 The Procter And Gamble Plaza Concentrated shampoo dosage of foam designating hair volume benefits
US10842720B2 (en) 2016-10-21 2020-11-24 The Procter And Gamble Company Dosage of foam comprising an anionic/zwitterionic surfactant mixture
CN109843258A (en) 2016-10-21 2019-06-04 宝洁公司 Indicate the concentrated type shampoo foam of hair conditioning benefit
WO2018075838A1 (en) 2016-10-21 2018-04-26 The Procter & Gamble Company Concentrated shampoo dosage of foam for providing hair care benefits
CN106675816A (en) * 2016-12-08 2017-05-17 湖北蕲艾堂科技有限公司 Laundry tablet and preparation method thereof
EP3579815B1 (en) * 2017-02-08 2020-07-01 Unilever PLC Xanthan structured high polyol liquid cleansers
US10675231B2 (en) 2017-02-17 2020-06-09 The Procter & Gamble Company Packaged personal cleansing product
US10806686B2 (en) 2017-02-17 2020-10-20 The Procter And Gamble Company Packaged personal cleansing product
US11224567B2 (en) 2017-06-06 2022-01-18 The Procter And Gamble Company Hair compositions comprising a cationic polymer/silicone mixture providing improved in-use wet feel
US11679073B2 (en) 2017-06-06 2023-06-20 The Procter & Gamble Company Hair compositions providing improved in-use wet feel
US11141370B2 (en) 2017-06-06 2021-10-12 The Procter And Gamble Company Hair compositions comprising a cationic polymer mixture and providing improved in-use wet feel
WO2019074988A1 (en) 2017-10-10 2019-04-18 The Procter & Gamble Company A method of treating hair or skin with a personal care composition in a foam form
CN111278418A (en) 2017-10-10 2020-06-12 宝洁公司 Compact shampoo composition with amino acid based anionic surfactant and cationic polymer
JP6945746B2 (en) 2017-10-10 2021-10-06 ザ プロクター アンド ギャンブル カンパニーThe Procter & Gamble Company Compact shampoo composition containing sulfate-free surfactant
WO2019074993A1 (en) 2017-10-10 2019-04-18 The Procter & Gamble Company Sulfate free clear personal cleansing composition comprising low inorganic salt
JP7280265B2 (en) 2017-12-20 2023-05-23 ザ プロクター アンド ギャンブル カンパニー Transparent shampoo composition containing silicone polymer
JP2021528410A (en) 2018-06-29 2021-10-21 ザ プロクター アンド ギャンブル カンパニーThe Procter & Gamble Company Low Surfactant Aerosol Antidandruff Composition
BR112021016099A8 (en) * 2019-02-15 2022-10-11 Johnson & Johnson Consumer Inc MOLDABLE GEL CLEANING LOTION
CN114746153A (en) 2019-12-06 2022-07-12 宝洁公司 Sulfate-free compositions with enhanced scalp active deposition
US11540980B2 (en) * 2019-12-20 2023-01-03 Colgate-Palmolive Company Personal care compositions and methods for the same
CN115151310A (en) 2020-02-27 2022-10-04 宝洁公司 Sulfur-containing anti-dandruff compositions with enhanced efficacy and aesthetics
US20220096338A1 (en) * 2020-09-30 2022-03-31 L'oreal Compositions and methods for styling hair
MX2023005963A (en) 2020-12-04 2023-06-07 Procter & Gamble Hair care compositions comprising malodor reduction materials.
US20220378684A1 (en) 2021-05-14 2022-12-01 The Procter & Gamble Company Shampoo Compositions Containing a Sulfate-Free Surfactant System and Sclerotium Gum Thickener
US11986543B2 (en) 2021-06-01 2024-05-21 The Procter & Gamble Company Rinse-off compositions with a surfactant system that is substantially free of sulfate-based surfactants
SE545486C2 (en) * 2021-07-15 2023-09-26 Bio Works Tech Ab Method for the manufacture of agar or agarose beads using vegetable oil

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1461775A (en) * 1973-04-27 1977-01-19 Unilever Ltd Detergent composition
US4543250A (en) * 1983-04-11 1985-09-24 Fmc Corporation Toiletry formulations comprising low molecular weight carrageenan
US5151210A (en) 1985-07-25 1992-09-29 The Procter & Gamble Company Shampoo compositions
US5089269A (en) * 1987-11-07 1992-02-18 Shiseido Company Ltd. Cosmetic containing fine soft microcapsules
LU86361A1 (en) 1986-03-19 1987-11-11 Oreal AQUEOUS COSMETIC COMPOSITION WITH DIFFERENT FOAM FOR THE TREATMENT OF HAIR AND SKIN
GB8628068D0 (en) 1986-11-24 1986-12-31 Unilever Plc Aqueous gel comprising carrageenan
EP0355908B1 (en) * 1988-08-17 1996-12-18 Unilever N.V. Liquid based composition comprising gelling polysaccharide capable of forming a reversible gel and a method for preparing such composition
ATE146504T1 (en) * 1988-08-17 1997-01-15 Unilever Nv LIQUID MIXTURE CONTAINING A POLYSACCHARIDE THICKENER CAPABILITY OF FORMING A REVERSIBLE GEL AND METHOD FOR THE PRODUCTION THEREOF
GB8926904D0 (en) 1989-11-28 1990-01-17 Unilever Plc Thickening system
GB8928370D0 (en) 1989-12-15 1990-02-21 Unilever Plc Fluid composition
DE4319699A1 (en) * 1993-06-16 1994-12-22 Henkel Kgaa Ultra mild surfactant blends
DE4319700A1 (en) * 1993-06-16 1994-12-22 Henkel Kgaa Ultra mild surfactant blends
DE4400632C1 (en) * 1994-01-12 1995-03-23 Henkel Kgaa Surfactant mixtures and compositions containing these
DE4435495C2 (en) * 1994-10-04 1997-08-14 Henkel Kgaa Pumpable aqueous surfactant concentrates
US5910472A (en) * 1994-12-03 1999-06-08 The Procter & Gamble Company Cleansing compositions
WO1996017582A1 (en) * 1994-12-05 1996-06-13 Permethyl Specialties L.L.C. Water soluble, biodegradable polymeric materials for skin care, hair care and cosmetic applications
CZ303797A3 (en) * 1995-03-29 1998-03-18 Unilever N. V. Liquid cleansing agent
JP3392980B2 (en) * 1995-04-10 2003-03-31 花王株式会社 Aqueous gel detergent composition
JPH08310942A (en) * 1995-05-19 1996-11-26 Kao Corp Aqueous gel-like detergent composition
CN1234751A (en) * 1996-08-26 1999-11-10 尤尼利弗公司 Aqueous solution composition comprising polymer hydrogel compositions
US5866529A (en) * 1996-09-20 1999-02-02 Colgate-Palmolive Co High foaming nonionic surfactant base liquid detergent comprising gelatin beads

Also Published As

Publication number Publication date
CA2324956A1 (en) 1999-10-14
ID26415A (en) 2000-12-21
PL343323A1 (en) 2001-08-13
HUP0102359A2 (en) 2001-10-28
KR100614161B1 (en) 2006-08-25
CA2324956C (en) 2008-06-17
WO1999051716A1 (en) 1999-10-14
MY120177A (en) 2005-09-30
US6329331B1 (en) 2001-12-11
BR9909395B1 (en) 2009-01-13
RU2217488C2 (en) 2003-11-27
KR20010042405A (en) 2001-05-25
JP2002510745A (en) 2002-04-09
CZ20003634A3 (en) 2001-12-12
AU749720B2 (en) 2002-07-04
EP1066366B1 (en) 2005-08-24
HK1038583A1 (en) 2002-03-22
AR014796A1 (en) 2001-03-28
DE69926872D1 (en) 2005-09-29
AU3519399A (en) 1999-10-25
ES2247796T3 (en) 2006-03-01
EP1066366A1 (en) 2001-01-10
PL191306B1 (en) 2006-04-28
JP4625580B2 (en) 2011-02-02
DE69926872T2 (en) 2006-05-18
US20010056049A1 (en) 2001-12-27
BR9909395A (en) 2000-12-05
CZ302724B6 (en) 2011-09-29
CN1230513C (en) 2005-12-07
GB9807269D0 (en) 1998-06-03
CN1296524A (en) 2001-05-23
HUP0102359A3 (en) 2002-08-28

Similar Documents

Publication Publication Date Title
EP1066366B1 (en) Detergent compositions
JP3925740B2 (en) A rod-shaped composition comprising a low-viscosity oil previously thickened with a non-foaming hydrophobic polymer
US9931282B2 (en) Liquid personal cleansing composition
US5851978A (en) Soap composition
EP0817608B1 (en) Liquid cleanser compositions
KR19980703589A (en) Surfactant composition
US6265368B1 (en) Aqueous detergent compositions thickened using carrageenan
WO1996002224A1 (en) Detergent composition
MXPA97004187A (en) Liquid cleanser for skin, stable to storage, containing polymer former of gel, lipid and crystalline ester of fatty acid and etilen gli

Legal Events

Date Code Title Description
FG Grant or registration